1. Field of the Invention
The present invention relates to structures containing a non-oriented multilayer film comprising a polyolefin core. The multilayer film is particularly useful as a protective coating for metal surfaces.
2. Description of Related Art
Multilayer polymeric films having polyolefin cores have utility, for example, as moisture barriers, adhesive structures, packaging materials, and as protective coatings for metal surfaces. The polyolefin core enhances the moisture barrier properties and flexibility of the film. Examples of multilayer polymeric films having polyolefin cores include those disclosed in the following U.S. patents.
U.S. Pat. No. 4,188,443 discloses an optically clear multilayer polyester/polyolefin shrink film. The shrink film is oriented after formation so as to establish shrink tension in at least one direction. Shrink tension is disadvantageous in a film coated on a substrate, such as a metal surface, since the film tends to delaminate from the substrate as the shrink tension is relieved.
U.S. Pat. No. 4,705,707 discloses a non-oriented, heat-sealable, co-extruded, three- or five-layer moisture barrier film. The film has an xe2x80x9cABCxe2x80x9d or xe2x80x9cABCBAxe2x80x9d structure where layer xe2x80x9cAxe2x80x9d is a polyester, copolyester or blend thereof. Unfortunately, polyesters and copolyesters do not offer optimal adhesion to modified polyolefin layers, tend to be costly, and tend to absorb moisture.
U.S. Pat. No. 4,716,061 discloses a non-oriented, heat-sealable, co-extruded, three- or five-layer moisture barrier film similar to U.S. Pat. No. 4,705,707 except where layer xe2x80x9cCxe2x80x9d comprises polypropylene instead of polyethylene.
U.S. Pat. No. 6,027,776 discloses a five-layer film useful for packaging and administering medical solutions. The five-layer film comprises an interior layer, first and second exterior layers, and first and second adhesive layers between the interior layer and the first and second exterior layers, respectively. The interior layer consists of homogeneous ethylene/alpha-olefin copolymer or blends of homogeneous ethylene/alpha-olefin copolymers. Homogeneous ethylene/alpha-olefin copolymers are more expensive than alternative polyolefins. Homogeneous ethylene/alpha-olefin copolymers also tend to be less thermally stable than heterogeneous polymers.
A multilayer film that has the moisture barrier properties and flexibility provided by a polyolefin core yet is non-oriented so as to minimize shrink tension is desirable. A non-oriented multilayer film further comprising an adhesive layer that overcomes the disadvantages listed for polyesters and copolyesters is even more desirable. Still more desirable is a non-oriented film further comprising a core layer that comprises a polymer other than a homogeneous ethylene/alpha-olefin copolymer.
The present invention is a structure comprising a non-oriented multilayer film, wherein said multilayer film comprises: (a) a first tie layer having opposing first and second surfaces; (b) a polyolefin core layer comprising 40 weight-percent or less homogeneous ethylene/alpha-olefin copolymer and having opposing first and second surfaces with the first surface of the core layer adhered to the first surface of the first tie layer; (c) a second tie layer having opposing first and second surfaces with the first surface of the second tie layer adhered to the second surface of the core layer; and (d) a first adhesive layer having opposing first and second surfaces with the first surface of the first adhesive layer adhered to the second surface of the second tie layer; the adhesive layer comprising a blend of polar-modified polyolefin and a polyester, copolyester, or polyester/copolyester blend. Additional layers, such as a second adhesive layer and a thermoplastic layer may be included in the multilayer film. The multilayered film may be adhered to a metal surface.
In a first preferred embodiment, the film of the present invention further comprises: (e) a second adhesive layer having opposing first and second surfaces with the first surface of the second adhesive layer adhered to the second surface of the first tie layer; (f) a thermoplastic layer comprising an oriented polyester and having opposing first and second surfaces with the first surface of the thermoplastic layer adhered to the second surface of the second adhesive layer; and (g) a primed metal surface to which the second surface of the first adhesive layer is adhered.
A second preferred embodiment is similar to the first preferred embodiment accept that thermoplastic layer (f) comprises a non-oriented amorphous or semicrystalline polyester, copolyester, or polyester/copolyester blend.
Designation of first and second surfaces herein is for ease of illustration. In general, the first and second surfaces are interchangeable so long as the surface of one layer is adhered to a proximate surface of an adjacent layer.
The film of the present invention advances the art by providing a non-oriented multilayer film with an adhesive layer comprising a blend of a polar-modified polyolefin and a polyester, copolyester, or polyester/copolyester blend and a polyolefin core layer that comprises 40 wt % or less homogeneous ethylene/alpha-olefin. The multilayer film of the present invention is particularly useful as a protective coating for metal surfaces.
xe2x80x9cNon-oriented multilayer filmxe2x80x9d refers to a multilayered film structure that is substantially free of post-formation orientation. However, individual layers of the non-oriented multilayer film may be oriented prior to creating the multilayered film structure. A non-oriented multilayer film structure does not include, for example, oriented multilayered shrink films.
xe2x80x9cHomogeneous ethylene/alpha-olefinxe2x80x9d and xe2x80x9chomogeneous ethylene/alpha-olefin copolymerxe2x80x9d refer to ethylene/alpha-olefin polymerization reaction products of relatively narrow molecular weight distribution (Mw/Mn) and relatively narrow composition distribution, as defined in U.S. Pat. No. 6,027,776 column 5, line 66 through column 7, line 22 (incorporated herein by reference). Homogeneous ethylene/alpha-olefin copolymers are structurally different from heterogeneous ethylene/alpha-olefin copolymers in that homogeneous ethylene/alpha-olefins exhibit a relatively even sequencing of comonomers within a chain, a mirroring of sequence distribution in all chains, and a similarity of length of all chains, i.e., a narrower Mw/Mn. Furthermore, homogeneous ethylene/alpha-olefin copolymers are typically prepared using metallocene, or other single-site type catalysts rather than Ziegler Natta catalysts. Homogeneous ethylene/alpha-olefin copolymers generally have a Mw/Mn of less than 2.7 (as determined by gel permeation chromatography, for example), a composition distribution breadth index greater than about 70 percent, and an essentially singular melting point characteristic with a peak melting point as determined by Differential Scanning Calorimetry of from about 60xc2x0 C. to about 110xc2x0 C.
xe2x80x9cHeterogeneous polyolefinxe2x80x9d refers to a polyolefin having a relatively wide Mw/Mn, prepared using conventional Ziegler-Natta or other heterogeneous catalysts. Heterogeneous catalysts contain several kinds of active sites which differ in Lewis acidity and steric environment. Examples of Ziegler-Natta heterogeneous catalysts include a metal halide activated by an organometallic co-catalyst, such as titanium chloride, optionally containing magnesium chloride, complexed to trialkyl aluminum. Homogeneous ethylene/alpha-olefins are not included in the definition of heterogeneous polyolefin.
Heterogeneous polyolefins can include, for example, polypropylene polymers and copolymers, linear low-density polyethylene, linear medium density polyethylene, very low-density polyethylene, ultra low-density polyethylene, and ethylene/alpha olefin resins wherein the ethylene is copolymerized with alpha-olefin monomers such as butene, hexene and octene.
Non-oriented multilayer film of the present invention comprise at least four layers: (a) a first tie layer; (b) a core layer; (c) a second tie layer; and (d) a first adhesive layer. Additional optional layers include a second adhesive layer and a thermoplastic layer. The non-oriented multilayer film of the present invention can also include an adhered metal surface. Typically, non-oriented multilayer films of the present invention are translucent as opposed to transparent.
A tie layer joins a core layer to another layer. Therefore, the tie layers must be adhesively compatible with the core layer and at least one other layer. For example, a tie layer can join a core layer to an adhesive layer, requiring that the tie layer be adhesively compatible with both the core layer and adhesive layer. A tie layer can join a core layer to a metal surface, requiring that the tie layer be adhesively compatible with both the core layer and metal surface. A tie layer can join a core layer to a thermoplastic layer, requiring the tie layer to be adhesively compatible with the core layer and thermoplastic layer. A layer is xe2x80x9cadhesively compatiblexe2x80x9d with a surface or layer if it can be adhered to that surface or layer.
The tie layers may be the same or different and comprise a polar-modified polyolefin. Polar-modified polyolefins include olefin polymers having a polar monomer copolymerized therein, an olefin polymer or copolymer grafted with an acid or anhydride, or derivatives thereof. Examples of suitable polar-modified polyolefins include ethylene/vinyl acetate copolymer (EVA); ethylene/methacrylate copolymer (EMA); ethylene/n-butyl acrylate (EnBA); ethylene/vinyl acetate/carbon monoxide (EVACO); ethylene/acrylic acid (EAA); ethylene/methacrylic acid (EMAA); ionomeric salts of ethylene/carboxylic acid copolymers such as sodium, zinc or potassium ionomers of EMAA or EAA; maleic anhydride grafted EVA (MAH-g-EVA); maleic anhydride grafted linear low-density polyethylene (MAH-g-LLDPE); and maleic anhydride grafted polypropylene (MAH-g-PP). The tie layer preferably comprises a maleic anhydride grafted polyolefin such as MAH-g-EVA, MAH-g-LLDPE, or MAH-g-PP. Preferably, the polyolefin contains at least 0.2 weight-percent (wt %) maleic anhydride (MAH), more preferably at least 0.5 wt % MAH, based on the weight of polyolefin and less than 2.0 wt %, preferably less than 1.6 wt % MAH based on the weight of polyolefin. MAH levels below 0.2 wt % impart insufficient polarity to the polyolefin for adhering to an adhesive layer, thermoplastic layer, or metal surface. MAH levels above 2.0 wt % results in tie layers having excess crosslinking and/or excessively high viscosity.
Suitable polyolefin resins for the tie layer have a specific gravity of from about 0.88 to about 1.1 grams per cubic centimeter (g/cm3). The resins have a viscosity of about 1 (one) to about 30 grams per 10 minutes (g/10 min.) as indicated by melt index (MI) measured according to American Society for Testing and Materials (ASTM) method D1238 (190xc2x0 C., 2.16 kg). Each tie layer preferably comprises at least 5 percent (%), more preferably at least 10%; and preferably less than 20%, more preferably less than 15% of the total multilayer film thickness. However, in no case will the tie layer thickness be less than about 0.2 mils (5 micrometers (xcexcm)). Layer thickness less than about 0.2 mils (5 xcexcm) are difficult to uniformly co-extrude and will provide insufficient interlayer adhesion between adjacent layers.
The core layer comprises a polyolefin resin and contains 40 wt % or less, preferably 25 wt % or less, more preferably 10 wt % or less homogeneous ethylene/alpha-olefin copolymer. The present invention may include a core layer that is essentially, or even completely, free of homogeneous ethylene/alpha-olefin copolymer. Preferably, the core layer comprises a heterogeneous polyolefin. Suitable polyolefin resins for the core layer include polyethylene (PE) homopolymers and copolymers, polypropylene (PP) homopolymers and copolymers, or blends thereof. More preferably, the polyolefin is linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), or PP (homopolymer or copolymer). The polyolefin resin in the core can be non-polar to enhance water-resistance. The core can be PP-free, if desired. Most preferably, the polyolefin resin in the core is LLDPE or HDPE. The core layer optionally contains compatiblizers, such as MAH-grafted polyolefins, to improve interlayer adhesion. Suitable polyolefin resins for the core layer have a specific gravity of from about 0.88 to about 1 (one) g/cm3. PE resins have a viscosity as indicated by a MI of from about 1 (one) to about 30 g/10 min., as determined by ASTM method D1238 (Conditions 190xc2x0 C., 2.16 kg). PP resins will have a viscosity as indicated by melt flow rate (MFR) of about 1 (one) to about 30 g/10 min., as determined by ASTM method D1238 (230xc2x0 C., 2.16 kg). Resins having a viscosity outside these ranges tend to be difficult to process.
A core layer preferably comprises at least 10%, more preferably at least 40%, and preferably less than 70% of a total multilayer film thickness. A core layer thickness below 10% of the total multilayer film thickness imparts inadequate film toughness and formability to the multilayer film. A core layer thickness greater than about 70% requires adjacent layers to be too thin to provide adequate interlayer cohesive strength. The core layer preferably exhibits an average melting point of greater than 100xc2x0 C. so as to not melt or significantly soften in boiling water. The xe2x80x9caverage melting pointxe2x80x9d is a weighted average of individual melting points of resins used in the core layer.
An adhesive layer can join a tie layer to an outer layer such as a thermoplastic layer or metal surface. Therefore, an adhesive layer is desirably adhesively compatible with a tie layer and an outer layer, preferably with a thermoplastic layer and/or a metal surface, more preferably with a thermoplastic layer and/or a primed metal surface. Adhesive layers, in films comprising more than one adhesive layer, can have the same composition or different compositions.
The adhesive layer comprises a blend of a polar-modified polyolefin, as defined for the tie layer, and a polyester, copolyester, or polyester/copolyester blend. The modified polyolefin can serve a number of purposes in the adhesive layer including increasing adhesive layer viscosity to improve adhesive layer distribution during co-extrusion, increase adhesive compatibility with the tie layer, decrease the cost of the adhesive layer, and improve moisture resistance of the adhesive layer. The polyester or copolyester component provides enhanced adhesion to an adjacent adhered polyester thermoplastic polymer surface layer and/or to a polyester primed metal surface. Additionally, the polyester or copolyester component can increase the average melting point of the adhesive layer composition. The adhesive layer is preferably solvent-free and desirably exhibits an average melting point greater than 100xc2x0 C. An adhesive layer having an average melting point below 100xc2x0 C. can melt, lose adhesive strength and delaminate in boiling water.
Typically, the polar-modified polyolefin comprises at least 10 weight-percent (wt %), preferably at least 20 wt %; and typically less than 70 wt %, preferably less than 60 wt % of the total adhesive layer. The polyester, copolyester, or polyester/copolyester blend component comprises at least 30 wt %, preferably at least 40 wt %; and typically less than 90 wt %, preferably less than 80 wt % of the total adhesive layer weight. If the polyester, copolyester, or polyester/copolyester blend is less than 30 wt % of the adhesive layer weight, the adhesive layer tends to have poor adhesion to primed metal surfaces and/or thermoplastic layers. If the polyester, copolyester, or polyester/copolyester blend is greater than 90 wt % of the adhesive layer weight, the adhesive layer tends to have poor adhesion to the tie layer. The polar-modified polyolefin and polyester, copolyester, or polyester/copolyester blend comprise 100 wt % of the adhesive layer, or less if additives are included.
The polyester and copolyester blend components comprise reaction products of terephthalic acid, isophthalic acid or adipic acid with ethylene glycol, butanediol or hexanediol. These polyester and copolyester resins exhibit melting point temperatures of from about 80xc2x0 C. to about 225xc2x0 C., preferably from about 100xc2x0 C. to about 150xc2x0 C.; and exhibit glass transition temperatures of from about xe2x88x9230xc2x0 C. to about 60xc2x0 C., preferably from about xe2x88x925xc2x0 C. to about 30xc2x0 C. The preferred polyester and copolyester resins have a relatively low weight-average molecular weight (Mw) of from about 10,000 to about 40,000, resulting in relatively low melt viscosities of from 100 to 2,000 Pascal-seconds (Pa-s) at 160xc2x0 C. and 2.16 kilogram (kg) (DIN/ISO 1133). Polyester and copolyester resins with the prescribed preferred properties are typically hot melt adhesive resins. Preferred copolyester components for the adhesive layer include those commercially available as GRILTEX(copyright) (trademark of EMS-CHEMIE) D1519, GRILTEX D1440, GRILTEX D1619, GRILTEX 6, and GRILTEX 9 copolyesters. Additional copolyester resins which are suitable for the adhesive layer composition are DYNAPOL(copyright) S copolyester (trademark of Huls Aktiengesellschaft), PLATHERM(copyright) copolyester (trademark of Elf Atochem North America), and copolyester hot melt adhesives from Bostik.
The multilayer film may contain a second adhesive layer, having first and second opposing surfaces, with the first surface of the second adhesive layer adhered to the second surface of the first tie layer. The second adhesive layer comprises a polar-modified polyolefin and a polyester, copolyester, or blend thereof as defined for the first adhesive layer. The composition of the second adhesive layer can be the same as or different from that of the first adhesive layer.
Each adhesive layer comprises at least 5%, preferably at least 10%; and preferably less than 20%, more preferably less than 15% of the total multilayer film thickness. Adhesive layers less than 5% of the total multilayer film thickness are insufficient for bonding the multilayer film to thermoplastic layers and/or metal surfaces. An adhesive layer thickness of at least 5% but less than 20% allows remaining layers to have enough film thickness to be effective.
Typically, a multilayer film of the present invention, in the absence of a thermoplastic polymer layer or metal surface, has a thickness of at least 1 mil (25.4 xcexcm), preferably at least 2 mils (50.8 xcexcm), more preferably at least 3 mils (76.2 xcexcm) and typically less than 20 mils (508 xcexcm), preferably less than 10 mils (254 xcexcm), more preferably less than 8 mils (203 xcexcm). A film having a thickness less than 1 mil (25.4 xcexcm) lacks desired scratch or abrasion resistance, moisture resistance, and coating durability and formability. Films thicker than 20 mils (508 xcexcm) are typically too soft to provide adequate surface hardness and difficult to form when laminated onto metal.
A multilayer film can comprise a first thermoplastic polymer layer adhered to the second surface of the first tie layer (in the absence of a second adhesive layer), the second surface of the first adhesive layer, or the second surface of a second adhesive layer.
The multilayer film may also comprise a second thermoplastic polymer layer wherein the first thermoplastic polymer layer is adhered to the second surface of first adhesive layer and the second thermoplastic polymer layer is adhered to the second surface of either a second adhesive layer or the first tie layer (in the absence of a second adhesive layer). The second thermoplastic polymer layer may be the same as or different from the first thermoplastic layer.
The first and second thermoplastic polymer layers can comprise any standard thermoplastic polymer. The thermoplastic polymer layers preferably provide a durable, relatively glossy, high modulus or stiffness, hard, easily cleaned, scratch resistant surface. Preferred polymers for the thermoplastic polymer layers include polystyrene (PS), oriented PS, oriented crystalline or semi-crystalline polyester and copolyester, oriented or non-oriented amorphous copolyester and polyester, oriented PP, oriented and non oriented polyamides, acrylics (such as polymethyl-methacrylate), and polycarbonates. More preferred polymers for the thermoplastic polymer layers include oriented crystalline and semi-crystalline polyester and oriented and non-oriented amorphous copolyester and polyester. The most preferred polymer is non-oriented amorphous polyester. In order to impart desired hardness, scratch resistance and stiffness to the multilayer film laminate, the thermoplastic polymer layer desirably exhibits a film tensile modulus (as determined by ASTM method D882) of at least 200,000 pounds-per-square-inch (psi) (1380 Mega-Pascals, MPa), preferably at least 250,000 psi (1725 Mpa). Typically, the thermoplastic polymer layers have a gauge of at least 0.4 mils (10 xcexcm), preferably at least 0.5 mils (13 xcexcm); and typically not more than 5.0 mils (127 xcexcm), preferably not more than 1.5 mils (38 xcexcm). Thermoplastic layers having a thickness below 0.4 mils (10 xcexcm) exhibit inadequate laminate scratch and abrasion resistance. Laminates with thermoplastic layer(s) thicker than 5 mils (127 xcexcm) typically exhibit excessive modulus or stiffness, resulting in a tendency toward curling of the laminate unless a thermoplastic film of similar modulus is on both sides of the laminate. Laminates with thermoplastic layers thicker than 5 mils (127 xcexcm) also tend to exhibit poor formability onto metal.
Adhere a thermoplastic layer to a multilayer film using any conventional means. Suitable means include direct coextrusion of the thermoplastic polymer layer as part of the multilayer film, extrusion coating of the thermoplastic polymer layer onto a previously produced multilayer film, extrusion of the thermoplastic polymer layer into a separate monolayer film and subsequently thermally laminating it onto the surface of the previously made multilayer film adhesive layer, or extrusion of the thermoplastic layer into a separate monolayer film and then adhering it to the previously made multilayer film using a liquid adhesive, such as a solvent-borne or an aqueous adhesive, or a low viscosity hot melt adhesive. If the thermoplastic polymer layer is a separate film and then subsequently adhered to the multilayer film, the thermoplastic polymer layer can be oriented (monoaxially or biaxially) or non-oriented.
One suitable thermoplastic polymer layer is a biaxially oriented polyester film, such as MYLAR(copyright) (trademark of E.I. du Pont de Nemours and Company), MELINEX(copyright) (trademark of E.I. du Pont de Nemours and Company), TERPHANE(copyright) (trademark of Toray Plastics Europe S.A.), HOSTAPHAN(copyright) (trademark of Hoechst Aktiengesellshaft) and DIAFOIL(copyright) (trademark of Diafoil Hoechst Co., LTD.). Modifying these films with a surface treatment for improving bonding or adhesion properties to a polyester is acceptable. Suitable surface treatments include corona, flame, or plasma treatment and coating with a surface coating, such as a copolyester or polyvinylidene chloride (PVDC) emulsion or dispersion.
Non-oriented amorphous or semi-crystalline polyester or copolyester films are also suitable as the thermoplastic layer. Suitable non-oriented amorphous or semi-crystalline polyester or copolyester films include monolayer films made from EASTAR(copyright) PETG 6763 copolyester, EASTAPAK(copyright) 9921 polyester or EASTOBOND(copyright) 19411 copolyester (EASTAR and EASTAPAK are trademarks of Eastman Chemical Company, EASTOBOND is a trademark of Eastman Kodak Company).
Optionally, the thermoplastic polymer layer and/or at least one layer of the multilayer film includes pigments or other conventional film additives such as anti-blocking agents, antioxidants or ultraviolet (UV) stabilizers, fire retardants, and fillers. Suitable pigments include titanium dioxide and carbon black, as well as conventional organic or inorganic colored pigments. Suitable fire retardants include chlorinated paraffin, antimony oxide, decabromodiphenyl oxide, aluminum trihydrate, and magnesium hydroxide. Suitable fillers include calcium carbonate. In one preferred embodiment, the core layer contains sufficient titanium dioxide to make the multilayer film both opaque and white.
Suitable techniques for preparing the multilayer film of the present invention include conventional tubular blown or slot die cast film processes. All of the layers can be prepared and laminated simultaneously into a single structure using a coextrusion feedblock. Non-limiting examples include simultaneous coextrusion of 4-layer xe2x80x9cABCBxe2x80x9d structures wherein the xe2x80x9cAxe2x80x9d layer is an adhesive layer, the xe2x80x9cBxe2x80x9d layers are tie layers, and the xe2x80x9cCxe2x80x9d layer is a core layer; xe2x80x9cABCB*xe2x80x9d structures wherein B and B* are different tie layers; symmetrical 5-layer xe2x80x9cABCBAxe2x80x9d structures; asymmetrical 5-layer xe2x80x9cABCBA*xe2x80x9d structures, wherein the xe2x80x9cAxe2x80x9d and xe2x80x9cA*xe2x80x9d layers are different adhesive layers differing in composition; and an asymmetrical xe2x80x9cABCB*A*xe2x80x9d structures comprising different tie layers xe2x80x9cBxe2x80x9d and xe2x80x9cB*xe2x80x9d and different adhesive layers xe2x80x9cAxe2x80x9d and xe2x80x9cA*xe2x80x9d.
Preparation and lamination of the multilayer film may comprise any of a number of sequential steps. For example, a symmetrical five-layer film having a first adhesive layer/first tie layer/core layer/second tie layer/second adhesive layer structure can be prepared in two steps: (a) co-extrude a first adhesive layer/first tie layer/core layer structure through a feedblock insert to divide the film into two symmetrical films; (b) melt bond together the core layers of the two symmetrical films prepared in step (a). Instead of using a feedblock insert, the co-extruded structure prepared in step (a) may be folded so as to contact the core layer with itself prior to melt bonding in step (b). A non-symmetrical five-layer film having a first adhesive-layer/first tie-layer/core-layer/second tie-layer/second adhesive-layer structure can be prepared in three steps: (a) co-extrude a first adhesive layer/first tie layer/core layer structure; (b) co-extrude a core layer/second tie layer/second adhesive layer structure; and (c) melt bond together the core layers of the structure prepared in steps (a) and (b).
A preferred non-oriented multilayer film of the present invention is adherable to a metal surface. For example, the second surface of the first adhesive layer, the second surface of a second adhesive layer, or the second surface of the first tie layer (in the absence of a second adhesive layer) can adhere to a metal surface.
One may also adhere the multilayer film to a first and second metal surface. The second surface of the first adhesive layer can be adhered to the first metal surface while the second surface of either a second adhesive layer or the first tie layer (in the absence of a second adhesive layer) can be adhered to the second metal surface.
One may adhere the multilayer film to both a metal surface and a thermoplastic polymer layer. For example, the second surface of the first adhesive layer may be adhered to a metal surface and the second surface of either a second adhesive layer or the first tie layer (in the absence of a second adhesive layer) may be adhered to a thermoplastic polymer layer. Alternatively, the second surface of the first adhesive layer may be adhered to a thermoplastic polymer layer and either the second surface of the second adhesive layer or the second surface of the first tie layer (in the absence of a second adhesive layer) may be adhered to a metal surface.
Suitable metal surfaces include non-primed and primed steel, zinc galvanized steel, tin-plated steel, and aluminum. The metal surfaces may comprise a chromate or phosphate-based surface treatment. Coating the metal surface prior to adhesion using solvent or aqueous-based primers is acceptable. Suitable primers include those that are epoxy-based such as epoxy-phosphate, epoxy-ester, epoxy-phenolic, epoxy-amine; and those that are polyester-based such as polyester-amine, polyester-melamine or polyester-melamine-formaldehyde. These primers can additionally contain passivating agents or pigments, such as powdered zinc and zinc chromate. Preferred metal surfaces include primed steel; and more preferred are steel primed with a polyester-based or epoxy-based primer; and most preferred are steel primed with polyester-melamine cured primers.
Typically, laminate films to primed steel at temperatures of 300-450xc2x0 F. (149-232xc2x0 C.). Once laminated to a metal surface, the layers of the multilayer film have an interlayer cohesive strength of at least 5 pounds per inch (lb/inch) (0.88 Newtons per millimeter (N/mm)), as determined by ASTM D-903. Similarly, the film, once adhered to a metal surface, exhibits peel strength values of greater than 5 lb/inch (0.88 Newtons per millimeter (N/mm)), as determined by the same ASTM method. The film preferably remains adhered to the metal in boiling water for at least 1 hour with no significant delamination, more preferably with absolutely no delamination occurring.
Preferably, once laminated to a metal surface, the film remains completely laminated to the metal surface through an xe2x80x9cAdhesion After Indentationxe2x80x9d test (European Coil Coating Association Test Methods Copyright 1996 ECCA-T6[1995]) which utilizes an Erichsen Ball test. Alternatively, one may use a similar procedure, known as the Olsen ball punch deformation test of metallic sheet (ASTM E643). The xe2x80x9cAdhesion After Indentationxe2x80x9d test procedure involves cutting the film laminate with a knife blade in an xe2x80x9cXxe2x80x9d pattern and then punch forming a dimple from the metal side, centered on the xe2x80x9cXxe2x80x9d pattern, leaving a base around the dimple. More preferably, the film remains completely laminated to the metal after immersing the cut and dimpled sample from the xe2x80x9cAdhesion After Indentationxe2x80x9d test in boiling water for 1 hour (Indented Boiling Water Test).
Generally, films of the present invention that contain a thermoplastic layer consisting essentially of non-oriented amorphous or semi-crystalline polyester or copolyester demonstrate better adhesion to the metal during the xe2x80x9cAdhesion After Indentationxe2x80x9d test and the subsequent Indented Boiling Water Test than films containing an oriented polyester thermoplastic layer. One possible explanation for the better performance of amorphous polyester, without being bound by theory, is that the amorphous polyester has less inherent stress than oriented polyester, allowing the amorphous polyester to be more flexible when deformed and undergo less conformational changes when heated. In contrast, oriented films comprising oriented polyester as the thermoplastic layer tend to shrink and delaminate from the metal during the Indented Boiling Water Test.
The following examples further illustrate, but do not limit, the invention.